CN115595803A - Ultra-soft radiation cross-linked foamed polyolefin elastomer artificial leather - Google Patents
Ultra-soft radiation cross-linked foamed polyolefin elastomer artificial leather Download PDFInfo
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- CN115595803A CN115595803A CN202110774192.1A CN202110774192A CN115595803A CN 115595803 A CN115595803 A CN 115595803A CN 202110774192 A CN202110774192 A CN 202110774192A CN 115595803 A CN115595803 A CN 115595803A
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- polyolefin elastomer
- artificial leather
- foamed
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Links
- 229920006124 polyolefin elastomer Polymers 0.000 title claims abstract description 88
- 239000002649 leather substitute Substances 0.000 title claims abstract description 47
- 230000005855 radiation Effects 0.000 title claims abstract description 45
- 238000005187 foaming Methods 0.000 claims abstract description 37
- 238000004132 cross linking Methods 0.000 claims abstract description 24
- 239000004814 polyurethane Substances 0.000 claims abstract description 24
- 229920002635 polyurethane Polymers 0.000 claims abstract description 23
- 238000002844 melting Methods 0.000 claims abstract description 7
- 230000008018 melting Effects 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000004088 foaming agent Substances 0.000 claims description 20
- 229920001971 elastomer Polymers 0.000 claims description 15
- 239000000806 elastomer Substances 0.000 claims description 8
- 239000005060 rubber Substances 0.000 claims description 7
- NBOCQTNZUPTTEI-UHFFFAOYSA-N 4-[4-(hydrazinesulfonyl)phenoxy]benzenesulfonohydrazide Chemical compound C1=CC(S(=O)(=O)NN)=CC=C1OC1=CC=C(S(=O)(=O)NN)C=C1 NBOCQTNZUPTTEI-UHFFFAOYSA-N 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- 238000010894 electron beam technology Methods 0.000 claims description 2
- 239000011527 polyurethane coating Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000010410 layer Substances 0.000 claims 17
- 230000005251 gamma ray Effects 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 6
- 239000000126 substance Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 10
- 239000002002 slurry Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- 239000004744 fabric Substances 0.000 description 7
- 229920002943 EPDM rubber Polymers 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000010985 leather Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical group [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- 229920001410 Microfiber Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 229920006213 ethylene-alphaolefin copolymer Polymers 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- -1 isocyanate ester Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0043—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers
- D06N3/005—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers obtained by blowing or swelling agent
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06N3/045—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds with polyolefin or polystyrene (co-)polymers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/06—Properties of the materials having thermal properties
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/14—Properties of the materials having chemical properties
- D06N2209/143—Inert, i.e. inert to chemical degradation, corrosion resistant
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/16—Properties of the materials having other properties
- D06N2209/1635—Elasticity
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/16—Properties of the materials having other properties
- D06N2209/1642—Hardnes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
The invention discloses super-soft radiation crosslinking foaming polyolefin elastomer artificial leather which sequentially comprises a polyurethane layer, a multi-layer polyolefin elastomer layer and a base layer attached to the polyolefin elastomer layer from top to bottom. Wherein the multilayer polyolefin elastomer layer comprises at least one foamed layer and at least one modified layer and is radiation crosslinked. The super-soft radiation cross-linking foaming polyolefin elastomer artificial leather prepared by the invention selects the polyolefin elastomer with the melting point less than or equal to 96 ℃ and the Shore A hardness less than or equal to 91, and has excellent temperature resistance, aging resistance and solvent resistance after cross-linking, and the polyolefin elastomer layer is softer in hand feeling, good in rebound resilience and lower in cost after foaming.
Description
Technical Field
The invention relates to the technical field of artificial leather, in particular to super-soft radiation crosslinking foaming polyolefin elastomer artificial leather.
Background
With the increasing living standard of people, people put forward higher and higher quality requirements on living goods. Leather, as an article of daily use, has been increasingly demanded not only in the market but also in various requirements (including environmental protection performance, inherent physical strength requirement, durability requirement, solvent resistance requirement, etc.) of customers in recent years. Because the genuine leather can produce a large amount of pollution in the manufacturing process, and meanwhile, the production cost is higher, the durability is relatively poor, the surface physical property is relatively low, the maintenance is difficult and other inherent defects exist, and the potential requirement of high quality of people cannot be met. Synthetic leather has been developed from the beginning to the present, and because of its advantages such as relatively excellent performance and relatively low cost, it has been used in the manufacture of shoes, bags, sofas, garments and other fields in large quantities, and the synthetic leather industry has become the pillar industry of the light industry.
At present, the structure of the whole synthetic leather is built on a base layer which takes Polyurethane (PU) or polyvinyl chloride (PVC) as a main body, a large amount of organic solvents and plasticizers, such as dimethylformamide, methyl ethyl ketone, acetone, toluene, ethyl acetate, o-benzene plasticizers and the like, are used in the production process, and the materials have great harm to human bodies or the environment.
Synthetic leather taking EVA as a base material structure is provided in my earlier patent, and has the advantages of good resilience, flexibility, aging resistance and the like, environmental friendliness, simple process, low cost and the like. But its high odor limits its range of use.
The polyolefin elastomer is odorless, has excellent aging resistance, is easy to process and can be crosslinked by organic or oxide, so that the polyolefin elastomer is widely applied to various fields, the low-hardness polyolefin elastomer is not reported to be applied to leather after radiation crosslinking and foaming, the cost of a product can be reduced by foaming the polyolefin elastomer, and the material is softer. Therefore, no report on how to utilize radiation crosslinking technology in the leather field while foaming polyolefin elastomers has been found.
Disclosure of Invention
The present invention has been made to overcome the above-mentioned drawbacks of the prior art and provides an ultra-soft radiation cross-linked foamed polyolefin elastomer artificial leather comprising, in order from top to bottom, a polyurethane layer, a multi-layered polyolefin elastomer layer, and a base layer attached to the polyolefin elastomer layer. Wherein the multilayer polyolefin elastomer layer comprises at least one foamed layer and at least one modified layer and is radiation crosslinked. The super-soft radiation crosslinking foaming polyolefin elastomer artificial leather prepared by the invention selects the polyolefin elastomer with the melting point of less than or equal to 96 ℃ and the Shore A hardness of less than or equal to 91, and has excellent temperature resistance, aging resistance and solvent resistance after crosslinking, and the polyolefin elastomer layer is softer in hand feeling, good in rebound resilience and lower in cost after foaming.
In order to achieve the above objects, the ultra-soft radiation cross-linked foamed polyolefin elastomer artificial leather of the present invention is mainly characterized in that the artificial leather comprises, in order from top to bottom, a polyurethane layer, a multi-layer polyolefin elastomer layer, and a base layer attached to the polyolefin elastomer layer. Wherein the multilayer polyolefin elastomer layer comprises at least one foamed layer and at least one modified layer and is radiation crosslinked.
Preferably, the base layer is any one of knitted elastic napped fabric, plain-knitted napped fabric, knitted plain fabric, woven polyester fabric, nylon fabric, microfiber base fabric, polyester filament elastic fabric, non-woven fabric, various other non-woven fabrics, and various papers.
Preferably, the modifying layer acts on the one hand to protect the foamed layer and on the other hand to impart specific properties thereto, such as: heat aging resistance, ultraviolet yellowing resistance, wear resistance and other properties.
Preferably, the matrix resin in the multilayer polyolefin elastomer foaming layer is a polyolefin elastomer, and the foaming layer comprises 100 parts of polyolefin elastomer, 1-15 parts of foaming agent, 0-100 parts of rubber elastomer, 0-10 parts of foaming promoter and other auxiliary agents and fillers.
Preferably, the polyolefin elastomer in the foaming layer is an ethylene-alpha olefin copolymer elastomer.
Preferably, the polyolefin elastomer has a melting point of less than or equal to 96 ℃ and a Shore A hardness of less than or equal to 91.
Preferably, the foaming agent in the foaming layer can be one or more than one of ADC foaming agent, OBSH foaming agent and bicarbonate.
Preferably, the foaming promoter can be one or more of zinc stearate, zinc oxide and zinc carbonate.
Preferably, the rubber elastomer includes, but is not limited to, natural Rubber (NR), ethylene-propylene-diene monomer (EPDM), hydrogenated styrene butadiene block copolymer (SEBS), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), and the like.
Preferably, the modified layer is a modified layer with special properties such as adhesion, resilience, wear resistance, softness and the like.
Preferably, the polyurethane layer is close to the modified layer, and the polyurethane layer can be a solvent-based, water-based or solvent-free polyurethane coating.
Preferably, the polyurethane layer is an environmentally friendly solvent-free or waterborne polyurethane type coating.
Preferably, the ultra-soft radiation cross-linked foamed polyolefin elastomer artificial leather adopts high-energy electron beams, gamma rays or X rays for radiation.
Preferably, the super-soft radiation crosslinking foaming polyolefin elastomer artificial leather has a foaming multiplying power of 1.2-10 times and a crosslinking degree of 15-90% of a multi-layer co-extrusion polyolefin elastomer layer.
Preferably, the total thickness of the synthetic leather is 0.21-5.3 mm, the thickness of the substrate layer is 0.1-2.2 mm, the thickness of the multi-layer polyolefin elastomer layer is 0.1-3.0 mm, the thickness of the polyurethane layer is 0.01-0.10 mm, and the thickness of each layer inside can be adjusted according to requirements.
Detailed Description
In order to more clearly describe the technical contents of the present invention, the following description will be further made with reference to specific examples, in which the amounts of the additives of each example and comparative example are the same for the sake of convenience in comparison with other additives and fillers which are not mentioned.
Example 1
In this embodiment, the polyurethane layer in the ultra-soft radiation cross-linked foamed polyolefin elastomer artificial leather is a conventional solvent-free polyurethane slurry formula, the multilayer polyolefin elastomer layer is a two-layer structure comprising a foaming layer and a modification layer 1, wherein the foaming layer is in contact with the base layer, the raw material formula of the foaming layer is shown in table one, wherein the foaming agent is an ADC foaming agent (weifang subsatellite L-C2), and the raw material formula of the modification layer 1 and the polyurethane layer slurry are respectively as follows:
modified layer 1
100 portions of polyolefin elastomer (Sanjing chemical DF740, melting point 96 ℃, shore A hardness 91)
0 portion of rubber elastomer (EPDM, the brand Dow 3745P)
Polyurethane layer
100 portions of solvent-free polyurethane prepolymer (Asahuan chemical XCJ 10A)
66.5 parts of curing agent (Asahi Chuan chemical XCJ 10B)
0.7 portion of catalyst (Bayer chemical T12)
Wherein the isocyanate ester content of the polyurethane prepolymer is 2.3 percent, and the hydroxyl value of the curing agent is 40mgKOH/g;
the invention also provides a preparation method of the super-soft radiation crosslinking foaming polyolefin elastomer artificial leather, wherein the irradiation dose and the thickness of each artificial layer are shown in the table II, and the method comprises the following steps:
1) Preparing related raw materials of a foaming layer and a modification layer;
2) Fully mixing the raw materials of the foaming layer and the modified layer, respectively adding the mixture into an extruder, extruding the mixture into a film, and laminating the film and the substrate layer together;
3) Foaming the multilayer polyolefin elastomer layer in a high-temperature furnace at a foaming temperature of 100-230 ℃;
4) A polyurethane layer is coated on the foamed multilayer polyolefin elastomer layer.
Finally, the super-soft radiation crosslinking foaming polyolefin elastomer artificial leather is prepared by the treatment of subsequent embossing, radiation crosslinking and the like.
Example 2
In this example, the ratio of the polyurethane layer slurry in the ultra-soft radiation cross-linked foamed polyolefin elastomer artificial leather and the preparation method thereof are the same as example 1, the multilayer polyolefin elastomer layer has a two-layer structure and comprises a foaming layer and a modification layer 1, wherein the foaming layer is in contact with the base layer, the raw material ratio of the foaming layer is shown in table one, the foaming agent is an ADC foaming agent (weifang yaxing L-C2), the irradiation dose and the thickness of each layer of the artificial leather are shown in table two, and the ratio of the modification layer 1 is shown in table two.
Modified layer 1
100 portions of polyolefin elastomer (Sanjing chemical DF 740)
100 portions of rubber elastomer (EPDM, the brand Dow 3745P)
Example 3
In this example, the ratio of the polyurethane layer slurry in the ultra-soft radiation cross-linked foamed polyolefin elastomer artificial leather and the preparation method thereof are the same as those in example 1, the multilayer polyolefin elastomer layer has a three-layer structure comprising a modified layer 2, a foamed layer and a modified layer 1, wherein the modified layer 2 is in contact with a base layer, the raw material ratio of the foamed layer is shown in table one, wherein the foaming agent is an ADC foaming agent (weifang asia star L-C2), and the irradiation dose and the thickness of each layer of the artificial leather are shown in table two. The raw material ratios of the modified layers 1 and 2 are as follows:
modified layer 1
100 portions of polyolefin elastomer (Sanjing chemical DF 740)
70 portions of rubber elastomer (EPDM, the brand Dow 3745P)
Modified layer 2
100 portions of polyolefin elastomer (Mitsui chemical DF 740)
6 portions of tackifying resin (terpene resin brand T100)
Example 4
In this example, the ratio of the polyurethane layer slurry in the multi-super-soft radiation cross-linked foamed polyolefin elastomer artificial leather and the preparation method are the same as example 1, the multi-layer polyolefin elastomer layer is of a three-layer structure and comprises a modified layer 2, a foamed layer and a modified layer 1, wherein the modified layer 2 is in contact with the base layer, the raw material ratio of the foamed layer is shown in table one in detail, the foaming agent is an ADC foaming agent (Weifang asiaxing L-C2), and the irradiation dose and the thickness of each layer of the artificial leather are shown in table two.
Modified layer 1
100 portions of polyolefin elastomer (Sanjing chemical DF 740)
50 portions of rubber elastomer (EPDM, the brand Dow 3745P)
Modified layer 2
100 portions of polyolefin elastomer (Sanjing chemical DF 740)
6 parts of tackifying resin (terpene resin brand T100)
Example 5
In this example, the slurry ratio of the modified layers 1 and 2 to the polyurethane layer in the ultra-soft radiation cross-linking foamed polyolefin elastomer artificial leather is adjusted to 100 to 160 ℃, the other preparation methods are the same as example 1, the multilayer polyolefin elastomer layer is a three-layer structure and comprises the modified layer 2, the foamed layer and the modified layer 1, wherein the modified layer 2 is in contact with the base layer, the raw material ratio of the foamed layer is detailed in table one, wherein the foaming agent is OBSH foaming agent (OBSH-75), and the irradiation dose and the thickness of each layer of the artificial leather are shown in table two.
Example 6
In this example, the slurry ratio of the modified layers 1 and 2 and the polyurethane layer in the ultra-soft radiation cross-linking foamed polyolefin elastomer artificial leather is adjusted to 100 to 200 ℃, the other preparation methods are the same as example 1, the multilayer polyolefin elastomer layer is a three-layer structure comprising the modified layer 2, the foamed layer and the modified layer 1, wherein the modified layer 2 is in contact with the base layer, the raw material ratio of the foamed layer is shown in table one, wherein the foaming agent is a sodium bicarbonate foaming agent (TR 60A, kunshan yayan science and technology), and the irradiation dose and the thickness of each layer of the artificial leather are shown in table two.
Example 7
In this example, the proportions of the modified layers 1 and 2 and the polyurethane layer slurry in the ultra-soft radiation cross-linking foamed polyolefin elastomer artificial leather are the same as those in example 4 except that the model of the polyolefin elastomer is changed to LG chemical LF100 (melting point 96 ℃, shore a hardness 91).
Example 8
In this embodiment, the proportions of the modified layers 1 and 2 and the polyurethane layer slurry in the ultra-soft radiation cross-linked foamed polyolefin elastomer artificial leather are the same as those in embodiment 4 except that the type of the polyolefin elastomer is changed to Mitsui chemical DF640 (melting point less than 50 ℃ C., shore A hardness 56).
Comparative example 1
The layer formulations and preparation were the same as in example 4 except that no foaming and irradiation was performed.
Comparative example 2
The layer formulations and preparation were the same as in example 4, with foaming but without irradiation.
TABLE-polyolefin elastomer foam layer Components parts by weight Table
Radiation dose and thickness table of each layer of super soft radiation crosslinking foaming polyolefin elastomer artificial leather
The data of the degree of cross-linking, shore hardness, and abrasion resistance of the foamed layer in the multi-layered polyolefin elastomer layer in the ultra-soft radiation cross-linked foamed polyolefin elastomer artificial leather manufactured in examples 1 to 8 and comparative examples 1 and 2 are shown in table three below. The degree of crosslinking of the foamed layer in the polyolefin elastomer layer was tested according to the xylene extraction method of GB/T29848-2018-5.5.3, abrasion resistance according to ASTM D1242-1995, and Shore hardness according to GB/T2411-2008.
Performance parameter table of surface three super soft radiation cross-linking foaming polyolefin elastomer artificial leather
It can be seen from the performance data of the table three super soft radiation cross-linked foamed polyolefin elastomer artificial leather, the degree of cross-linking of the foamed layer of the polyolefin elastomer can be adjusted by adjusting the amount of the cross-linking agent, the radiation dose and the foaming time by adopting the super soft radiation cross-linked foamed polyolefin elastomer artificial leather prepared by the invention. The super-soft radiation crosslinking foaming polyolefin elastomer artificial leather prepared by the invention has excellent temperature resistance, aging resistance and solvent resistance after crosslinking, and the polyolefin elastomer layer is softer in hand feeling, good in rebound resilience and lower in cost after foaming.
In this specification, the invention has been described with reference to specific embodiments thereof. It will, however, be evident that various modifications and changes may be made thereto without departing from the broader spirit and scope of the invention. The description is thus to be regarded as illustrative instead of limiting.
Claims (8)
1. The super-soft radiation cross-linked foamed artificial leather with polyolefin elastomer is characterized by comprising a polyurethane layer, a multi-layer polyolefin elastomer layer and a base layer attached to the polyolefin elastomer layer from top to bottom in sequence. Wherein the multilayer polyolefin elastomer layer comprises at least one foamed layer and at least one modified layer and is radiation crosslinked.
2. The artificial leather with super-soft radiation cross-linked and foamed polyolefin elastomer as claimed in claim 1, wherein the foamed layer comprises 100 parts of polyolefin elastomer, 1-15 parts of foaming agent, 0-100 parts of rubber elastomer, 0-10 parts of foaming promoter and other additives and fillers.
3. The artificial leather made of the ultra-soft radiation crosslinked foamed polyolefin elastomer according to claims 1 and 2, wherein the polyolefin elastomer is a polyolefin elastomer with a melting point of 96 ℃ or less and a Shore A hardness of 91 or less.
4. The ultra-soft radiation cross-linked foamed polyolefin elastomer artificial leather according to claims 1 and 2, wherein the foaming agent is one or a combination of more than one of ADC foaming agent, OBSH foaming agent, bicarbonate and the like.
5. The ultra-soft radiation cross-linked foamed polyolefin elastomer artificial leather according to claim 1, wherein said radiation employs high energy electron beam, gamma ray or X-ray.
6. The ultra-soft radiation cross-linked expanded polyolefin elastomer artificial leather according to claim 1, wherein the degree of cross-linking of the expanded layer in the multi-layered polyolefin elastomer layer is 15 to 90%.
7. The ultra-soft radiation cross-linked foamed polyolefin elastomer artificial leather according to claim 1, wherein the polyurethane layer is a solvent-based, water-based or solvent-free polyurethane coating layer.
8. The ultra-soft radiation cross-linked foamed polyolefin elastomer artificial leather according to claim 1, wherein the total thickness of the artificial leather is 0.21 to 5.3mm, the thickness of the base layer is 0.1 to 2.2mm, the thickness of the multi-layer foamed polyolefin elastomer layer is 0.1 to 3.0mm, and the thickness of the polyurethane layer is 0.01 to 0.10mm.
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| CN202110774192.1A CN115595803B (en) | 2021-07-08 | 2021-07-08 | Ultra-soft radiation crosslinked foaming polyolefin elastomer artificial leather |
| PCT/CN2021/131505 WO2023279625A1 (en) | 2021-07-08 | 2021-11-18 | Artificial leather and manufacturing method therefor |
| EP21949110.7A EP4342670A1 (en) | 2021-07-08 | 2021-11-18 | Artificial leather and manufacturing method therefor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1205669A (en) * | 1995-12-21 | 1999-01-20 | 陶氏化学公司 | Process for preparing laminate |
| CN111055570A (en) * | 2018-10-17 | 2020-04-24 | 贝内克-长顺汽车内饰材料（张家港）有限公司 | TPO composition for forming TPO artificial leather and corresponding TPO artificial leather |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1205669A (en) * | 1995-12-21 | 1999-01-20 | 陶氏化学公司 | Process for preparing laminate |
| CN111055570A (en) * | 2018-10-17 | 2020-04-24 | 贝内克-长顺汽车内饰材料（张家港）有限公司 | TPO composition for forming TPO artificial leather and corresponding TPO artificial leather |
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